For example, if the position is mostly coding C then just get them to explain how some X interacts with some Y and how that interacts with some Z. Maybe with a copy of of K&R and get them to point to page so and so.
Do that a few times, maybe use a whiteboard, and I think any experienced C developer will be able to tell who's faking it and who really understands within 2 or 3 iterations.
Even if there are no experienced folks in the company, then it will take longer but, after an hour or two it'd be pretty difficult for anyone to fake a solid understanding of hundreds of pages of K&R.